Theoretical Evidence for a NH···XC Blue-Shifting Hydrogen Bond:  Complexes Pairing Monohalomethanes with HNO

Document Type

Article

Journal/Book Title

Journal of Physical Chemistry A

Publication Date

2007

Publisher

American Chemical Society

Volume

111

Issue

20

First Page

4431

Last Page

4435

Abstract

Correlated ab initio calculations are used to analyze the interaction between nitrosyl hydride (HNO) and CH3X (X = F, Cl, Br). Three minima are located on the potential energy surface of each complex. The more strongly bound contains a NH···X bond, along with CH···O; CH···O and CH···N bonds occur in the less stable minimum. Binding energies of the global minimum lie in the range of 11−13 kJ/mol, and there is little sensitivity to the identity of the halogen atom. Unlike most other such hydrogen bonds, the NH covalent bond in this set of complexes becomes shorter, and its stretching frequency shifts to the blue, upon forming the NH···X hydrogen bond. The amount of this blue shift varies in the order F > Cl > Br.

Comments

Originally published by American Chemical Society in the Journal of Physical Chemistry.

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